Esters of acetylenic acids and polyhydric alcohols



3,082,242 Patented Mar. 19, 1963 3,082,242 ESTERS F ACETYLENIC ACIDS ANDPOLYHYDRIC ALCOHOLS Lee A. Miller and John M. Butler, Dayton, Ohio,assignors to Monsanto Chemical Company, St. Louis, Mo.,

a corporation of Delaware No Drawing. Filed June 23, 1960, Ser. No..38,113 10 Claims. (Cl. 260-486) The present invention relates to estersandmore particularly provides'esters of certain dior polyhydric alcoholsand certain acetylem'c acids and the method of preparing the same.

An object of the invention is the provision of-new and valuableacetylenic esters. Another object of the invention is the provision ofesters of acetylenic acids and polyhydroxy compounds. Still anotherobject of the invention is the provision of partial esters ofpolyhydroxy compounds and certain acetylenic acids. A further object isthe provision of completely esterified polyhydroxy compounds wherein theacid portions of the ester are derived from an acetylenic acid. Animportant objective of the invention is the provision of a methodwhereby the partially or completely esterified polyhydroxy compounds areprepared from an alkynoic acid compound. Still anotheriobjective of theinvention is to provide, from the acetylenic acids, esters havingbiological toxicant utility, i.e., compounds which will serve as theessential effective ingredients of fungicidal and bactericidalcompositions. The method of inhibiting the growth of microorganismsand/or of plant life wherein "there are employed compositions comprisingthe presently provided esters is a further objective of the invention.

These and other objects hereinafter defined are provided by theinvention wherein there are prepared new and valuable esters of theformula where R is selected from the class consisting of hydrocarbonradicals and halohydrocarbon radicals of from 2 to 18 carbon atoms andis linked through diverse carbon atoms thereof to the remainder of themolecule of which it forms a part, -n is an integer of from 0 to 3, m isan integer of from 1 to 4 and the sum of 11 plus m is from 2 to 4, and Zis selected from the class consisting of hydrogen, alkyl radicals offrom 1 to 5 carbon atoms and aryl radicals of from 6 to 10 carbon611011184" The presently provided acetylenic esters are'prepared byreaction of a polyhydric compoundofdhe formula R(0H.) wherein R is theabove defined hydrocarbon or halohydrocarbon radical and x is an integerof from 2 to 4 with a compound selected from the class consisting ofacetylenic acids of the formula ZCECOOH wherein Z is as above definedand acyl halides and anhydrides thereof, employing the reactionconditions which will be hereinafter described.

The presently useful dior polyhydric compounds may be the aliphatichydrocarbon or halohydrocarbon polyols having from 2 to 4 hydroxyradicals and a total of from 2 to 18 carbon atoms, e.g., the glycolssuch as ethylene glycol,

1,2- or 1,3-propanediol,

1,2-, 1,3-, 1,4- or 2,3-butanediol, 1,3-, 1,4-, 1,5-, 2,3- or2,4-pcntanediol, 2-butene-1,2-diol,

2-butene-1,4-diol, Z-bromo-l,3-propanediol, 2-fluoro-1,3-propanediol,2-hydroxymethyl-1,2,3-propanetriol, 2-butyne-l,4-diol,2-methyl-l,5-pentanediol,

- 2 1,4-dichloro-2,3-butanediol, 2,3-dibromo-1,4-butanediol, 2- or4-chloro-1,3-butanediol, 2,4-dimethyl-2,4-pentanediol,I,l,l-trifluoro-2,3-butanediol, 2,2-diethyl-L4-butanediol,

2-pentyn-1,4diol,

2-pentene-1,5-diol,

2-propyl-1,3-butanediol, Z-chIorO-LS-pentanediol, 5-iodo-1,4-hexanediol,

1,4-heXanediol,

5-methyl-l,2-hexanediol, 2-ethyl-l,3-hexanediol,2-tert-butyl-3,3,4,4-tetramethyl-1,2-pentanediol,4-methyl-l,4-hexanediol,

' 1,6-hexanediol' I 3,3-dimethyl-1,6-hexanediol, 2,4-dimethyl3-hexene-2,S-diol,

2,3-, 2,4-, 2,5-, or 3,4-hexanediol,

1,2,5-, 1,2,6-, 1,3,5-, 1,4,5-, 01'' 2,3,4-hexanetriol,l-chloro-2,5-dimethyl-3-hexyne-2,S-diol, l,2,3,6-hexanetetrol,2,4-hexadiyne-l,6-diol,

1,6-, 1,7-, 2,4-, or 2,5-heptenediol, 2'heptene-1,6-diol,1-chloro-2,5-dimethyl-3-heptyne-2,5-diol,S-ethyl-3-methyl-2,4-heptanediol, 4-ethyl-1,4,5-heptanetriol,3,6-dimethyl-2,3,6-heptanetriol,

1,2-, 1,3-, 1,4-, 1,8-, 2,4-, 2,7-, or 4,5-octanediol,2-methyl-2-octene-1,4-diol, 3-(hydroxymethyl)-1,5-pentanediol,2,4,4,S,5,7-hexamethyl-3,6-octanediol, 2,7-dimethyl-4-octane-2,7-diol,2-butyl-2-ethyl-4-methyl-1,3-octanediol,2,3,6,7-tetramethyl-2,3,6,7-octanetetrol, 3-heptafluoropropyl-1,5-pentanediol, 1,9-nonanediol,

1,2- or 1,10-decanediol, 2,3,8,9-tetramethyl 2,3,8,9-decanetetrol, 1,2-or 1,12-dodecanediol, 5-decyne-4,7-diol,4,7-dipropyl-5-decyne-3,4,7,8-tetro1, 5,9-dimethyl-8-decene-1,S-diol,5,8-diethyl-6,7-dodecanediol, 9-octadecenel 12-diol,

9,10- or 1,12-octadecanediol, 1,9,10-octadecanetriol,

1,9- or 1,11-undecanediol; 1,13-tridecanediol;

1,2-tetradecanediol,

1,2- or 1,16-hexadecanediol, 16-methyl-1,2-heptadecanediol,

1,2- or 1,12-octadecanediol, 2-methyl-1,2-propanediol,2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,2-ethyl-2-(hydroxymethyl)-1-3-propanediol,2-(hydroxymethyl)-2-methylpropanediol; 2-isobutyl-l,3-propanediol;

glycerine,

2-ethyl-1,3-butanediol, 2,2-diethyl-1,4-butanediol,2,2,3,3-tetramethyl-1,4-butanediol, pinacol,

erythritrol,

pentaerythritol,

1,2,3- or 1,2,4-butanetriol, 3-neopentylidene-1,5-pentanediol,

3 2-tert-butyl-1,2,5 pentanctriol, 1,3,4-, 1,3,5- or 2,3,4-pentanetriol,etc.

Examples of benzenoid dior polyols which are useful for esterificationwith the acetylenic acid, halide or anhydride are a o, m, orp-xylene-a,a'-dio1s, 3,6-dimethyl-o-xylene-a,a-diol,a,a'-dimethyl-p-xylene-a,a-diol, 1,6-diphenyl-1,6-hexanediol,6-phenyl-4,5,6-decanetriol, 1,2-diphenyl-l,2-ethanediol,

1- or 2-phenyl-1,2-propancdiol, 2-methyl-l-phenyl-1,2-propanediol,2-di-o-tolylmethyl-1,3-propanediol,

1- or 2-phenyl-1,2,3-propanetriol, 2-methyl-3-phenyl-1,2-butanedi0l,

1,4- or 2,2-diphenyl-1,4-butanediol,2,3-dimethyl-1,4-diphenyl-l,4-butanediol,S-methyl-l-phenyl-1,2,3-butanetriol, 1,6- or l,S-naphthalenedimethanol,a,a -mesitylenediol, a ,a ,u -mesitylenetriol-o-benzenediethanol,a,m'-dimcthylhydrobenzoin, 2,3-dibenzylidene-1,4-butanediol, 1,1-bis(p-bromophenyl)-2-butyne-l,4-diol, 1-phenyll,5-pentanediol,hydroquinone,

resorcinol,

2,6-dichlororesorcinol,

pyrocatechol, 4-tert-butyl-S-chloropyrocatechol, 4-dodecylpyrocatechol,

pyrogallol,

phloroglucinol,

1,2,4-benzenetriol, benzenetrimethanol,

l,2,3,4- or 1,2,3,5-benzenetetrol,

1 ,2,4,ibenzenetetramethanol,

.m, m'- or p, p'-biphenol, 4,4'-dichloro-o,o-biphenol,2,2,6,6'-tetraisopropyl-p,p-biphenol, 1,8- or 1,2-naphthalenediol;2-brorno-3-methyl-1,4-naphthalenediol, 4,4'-p-terphenyldiol, etc.

Alicyclic hydroxy compounds of present utility are, for example,

\ (bicyclohexyl) -1,1'-dimethanol,

2-( l-hydroxycyclohexyl)-5-methyl 3 hexene-2,5-diol,4-cyclohexylresorcinol,

1,3 ,5 -cyclohexanetriol, V 3,6-dibromo-4-cyclohexene-1,Z-diol,4,5-dimethyl-4-cyclohexene-1,2-dimethanol, etc.

The acetylenic acids which are reacted with the polyols to give thepresently provided esters have the formula ZC.= CO0H wherein Z isselected from the class consisting of hydrogen, alkyl radicals of from 1to 5 carbon atoms and aromatic hydrocarbon radicals of from 6 to 10carbon atoms. Acyl halides or anhydrides of such acetylcnic acids may beused instead of the acids. The following are some of the presentlyuseful acetylenic acid compounds: propiolic acid, propiolyl chloride,bromide, iodide or fluoride, propiolic anhydride, tetrolic acid, 2-pentynoic acid, Z-hexynoic acid, 2-heptynoic acid, 2- octynoic acid,Z-octynoyl chloride, trimethyltetrolic acid, phenylpropiolic acid,phenylpropiolyl chloride, 2,3,4,6- tetramethylphenylpropiolic acid, 0-,mor p-tolylpropiolic acid, l-naphthalenepropiolic acid,4-phenyl-2-butynoic acid, etc.

The propiolyl halide to be used as one of the reactants of theesterification reaction may be prepared by reacting propiolic acid withbenzoyl halide. The reaction between benzoyl halide and propiolic acidis almost instantaneous at ambient temperature and being an equilibriumreaction it is desirable to remove one of the product materials duringthe course of the reaction in order to shift equilibrium in the desireddirection. In this respect propiolyl halide is relatively more volatilethan other materials in the reaction mass and for that reason thetemperature of reaction is controlled to cause substantial vaporizationof the propiolyl halide during the course of the reaction. Thepreparation of propiolyl chloride according to this procedure forms thesubject of the copending application of Lee A. Miller, Serial No. 6,344,filed February 3, 1960. The propiolyl chloride so formed may be leddirectly, without intermediate recovery, into a solution or suspensionof the polylol which is to be esterified according to this invention.

Reaction of the polyhydroxy compound with the alkynoic acid, or acylhalide or anhydride thereof takes place readily by simply contacting theacidic compound with the polyhydroxy compound at ordinary or increasedtemperature in the presence of an inert diluent or solvent.Advantageously, when the acetylenic acid is used, reaction is effectedat a temperature of from, say, 50' C. to C. and the heating within thistemperature is conducted until the desired extent of esterification hasoccurred. Using the acyl halide, optimum conditions include operation attemperatures which may be as low as, say, --10 C., i.e., extraneousheating is unnecessary; instead, cooling may be employed. The ratio ofacid compound to polyhydroxy compound which is employed will, of course,depend upon the number of hydroxy groups of the polyol which it isdesired to esterify, and it is advantageous to employ the reactants insuch stoichiometric proportion. However, a slight excess of either thepolyol or the acid compound may be used. Generally, the reactionproceeds with primary formation of the monoester and subsequently theother hydroxy radical or radicals of the polyol are progressivelyesterified, provided enough of the alkynoic acid compound is present inthe reaction mixture. Accordingly, the nature of the ester product willdepend to some extent upon reaction time. Thus, in order to obtain aproduct which is substantially a mono-ester, the reaction isdiscontinued when the quantity of evolved by-product is that calculatedfor mono-esterification. In this case, any excess of alkynoic acidcompound which is present is removed from the reaction mixture, e.g., bydistillation or solvent extraction. Thus, whether or not the reactantsare present in the stoichiometric proportions, the reaction time is afactor in obtaining the desired degree of esterification. However, itdoes not appear to be a substantial factor in obtaining good yields ofthe completely esterified product.

The presence of an inert diluent or solvent and operation at atemperature which is below 120 C. are both recommended for obtaining thepresently provided, well characterized esters in good yields. When thetemperature is increased and the diluent is omitted, there are producedreaction products which do not at all resemble the well-defined, thinlyliquid or crystalline esters of the present inventionginstead, theproducts are either heterogeneous masses, e.g., resinous materialsinterspersed with waxy products, or black tars, heavy oils or resinsdepending upon the nature of the individual reactants and upon theextent of variation from the reaction conditions which we have found tobe conducive to the production of the mono-, di-, trior tetra-alkynoatesor aralkynoates. Use of temperatures below 120 C. and operation in thepresence of 'a diluent apparently permits substantial limitation of thereaction to esterification, rather than to other reactions which couldbe expected to occur with the highly active triple bonded acidiccompounds and the bifunctional hydroxy compounds, e.g., addition of thehydroxy radical across the triple bond of the acidic component,polymerization of the acidic compound, linear condensation of the polyolthrough etherification, etc.

Inert liquid diluents which are' useful for the present purpose areliquid hydrocarbons generally, halogenated hydrocarbons, ethers, orketones, e.g., benzene, toluene, xylene, hexane, petroleum spirits,dichlorobenzene, ethylene dichloride, carbon tetrachloride,tetrachlorohexane, dioxane, isopropyl ether, acetone, butanone, etc. Thesolvent or diluent, of course, serves to facilitate uniform distributionof the reactants throughout the reaction medium. When reacting anacetylenic acyl halide with the polyol, it is preferred to employ asolvent or diluent which minimizes the tendency of the hydrogen halidebyproduct to react with the triple bond of the propiolic acid compound.In this connection the solvent or diluent is selected on the basis ofbeing the least compatible or having the poorest solvency for hydrogenhalide. The preferred solvents or diluents for this purpose. may be thecycloalkanes, e.g., cy'clohexane, cyclopentane or the alkyl substitutedcycloalkanes, etc., and the halogenated hydrocarbons.

When using the acetylenic acid as the starting material in theesterification reaction, water is formed as a byproduct material. Sincethe reaction is of the equilibrium type, it is preferred that theby-product water be removed continuously during the course of thereaction in order to have the equilibrium shift in the desireddirection. The solvent or diluent employed in the reaction may beselected on the basis that it will form an azeotrope with water or thatit boils above water, and thus the temperature of reaction can bemaintained at a level which facilitates removal of the water withoutaffecting the solvent or diluent. Considering the prerequisites of asolvent or diluent, generally any organic material which is nonreactivewith either the reactants or the product materials may be employed. Thequantity of solvent or diluent employed in the reaction variesconsiderably depending upon the result which is desired. In someinstances it may be desirable to employ a relatively small quantity ofdiluent as compared to the amount of reactants which are being used,whereas in other cases it may be desirable to use a relatively largequantity of solvent or diluent to facilitate intermixing of thereactants.

We have also found that when effecting the reaction with the free acidor the acid anhydride as the acetylenic acid component, it isadvantageous to operate in the presence of an acidic material ascatalyst. Acids which are useful for this purpose are, e.g., the mineralacids such as sulfuric, hydrochloric, nitric or phosphoric acid, orchlorosulfonic acid, acidic salts such as ferric chloride or magnesiumbisulfate, organic sulfonic acids such as benzenesulfonic acid or4-toluenesulfonic acid, etc.

Acetylenic esters provided by the invention are, e.g., the monoesters ofpolyols such as the propiolate, tetrolate, 2-hexynoate, 2-octy-noate,phenylpropiolate, 1- naphthylpropiolate of such polyols as ethyleneglycol,

propylene glycol, 2,3-dimethyl-l,3pentanediol, 1,4-butanediol,1,2-hexanediol, 2-bromo1,3-propanediol, 1,3- dichloro-2,3-butanediol,2,5adiheptanediol, 2-methyl-2- octane-1,4-diol, 1,2-dodecanediol,5-decyne-3,7-diol, glycerine, 1,2,3,6-hexanetetrol,4,7dipropyl-5-decyne-3,4,7,8- tetrol, 1,9,l0-octadecanetriol,Z-(hydroxymethyl) 2- methylpropanediol, erythritol, pentaerythritol,pyrocatechol, l,2-diphenyl-1,2-ethanediol,3,6-dimethyl-O-xylenea,a'di0l, 1,2,4-benzenetriol, p,p'-diphenol,1,2-naphthalenediol, 1,Z-dimethyl-1,2-cyclohexanediol,1,3,5-cyelohexanetriol, l,2-cyclopentanedimethanol, cy'clohexyl-1,2-

ethanediol, etc.

As examples of the presently provided di-, tri or tetraestrified polyolsare:

3-butene-1,4-diol dipropiolate Ethylene glycol ditetrolate.2,3-dimethyl-1,3-pentanediol di-2-pentynoate Propylene glycoldipropiolate 2-methyl-1,5-pentanediol bis(phenylpropiolate)2-heptene-1,6-diol dipropiolate l,6-methyl-1,Z-heptadec-anedioldi-Z-pentynoate I-Iydroquinone dipropiolate o-Benzenediethanolbis(phenylpropiolate) 1-phenyl-1,2-propaned-iol dipropiolate Glycerinedipropiolate Glycerine tripropiolate 4-ethyl-1,4,5-heptanetrioldipropiolate 4,4-dichloro-o,o-biphenol dipropiolate Pyrogalloltri-Z-hepty'noate l,2,3,4-benzenetetrol tetrapropiolate2,3,6,7-tetramethyl-2,3,6,7-octanetetrol tritetrolate Phloroglucinoldipropiolate Pentaerythritol tetrapropiolate Dicyclo-p,p'-hexanoldipropiolate 1,2-cyclopentanediol bis(phenylpropiolate)4-cyclohexene-l,2-dimethanol di-Z-pentynoatel-methyl-l,2,4-cyclohexanetrioldi-2-octynoate 1,l-cyclopropanedimethanoldipropiolate Cyclohexyl-l,2-ethanediol bis(phenypropiolate)3-cyclopentene-1,2-diol bis( l-naphthalenepropiolate)Decahydro-Z,S-naphthalenedimethanol dipropiolate2-methyl-1,2-propanediol dipropiolate 1,13-tridecanetriolbis(phenylpropiolate) 2-methyl-2octene-l,4-diol dipropiolate1,6-hexanediol bis(4-tolylpropiolate) A convenient method of preparingpartial esters having an alkynoate or arylalkynoate radical is by theaddition reaction of an alkylene oxide with the acetylenic acid, thus:

Reaction of the alkylene oxide with the acetylenic acid is conducted bysimply introducing the alkylene oxide'into a solution or suspension ofthe acetylenic acid at ordinary or moderately increased temperatures andin the pres ence or absence of a basic agent as catalyst. Temperaturesof from, say, l5 C. to 50 C. are advantageously employed. Basiccatalystsuseful in the addition reaction are organic or inorganic basicmaterials generally, e.g., the alkali metal alkoxides such as sodiummethoxide, the quaternary ammonium halides, such as trimethylbenzylammonium chloride, the heterocyclic bases such as pyridine or quinoline,the alkali metals or the oxides, hydroxides or basic salts thereof suchas sodium, potassium, lithium, or rubidium oxide, hydroxide, orcarbonate, ammonium hydroxide etc.

Solvents or diluents of general utility are liquids which are inertduring the reaction conditions, e.g., the hydrocarbon solvents such asbenzene or hexane; the chlorinated hydrocarbons such as carbontetrachloride or ethylene dichloride; the aliphatic or cyclic etherssuch as ethyl ether, butyl methyl ether or dioxane, etc.

Useful alkylene oxides include, e.g., ethylene oxide, propylene oxide,2,3-epoxy-2,4,4-trimethylpentane, 1,2- epoxy-Z-methylpropane,2,3-epoxybutane, 2,3-epoxypentane, l,2-epoxy-2,4,4-trimethylpentane,1,2-epoxypentane, 2,3-epoxyoctane, etc. The useful aeetylenic acids arethose which are disclosed above to be useful in esterification ofpolyhydroxy compounds. The partial esters obtained by reaction of thealkylene oxide with the acetylenic acids can be characterized generallyas hydroxyalkyl alkynoates or arylalkynoates, e.g., from ethylene oxideand phcnylpropiolic acid there is obtained hydroxyethylphenylpropiolate; from propylene oxide and propiolic acid there isobtained a mixture of 2-hydroxypropyl and l-(hydroxymethyl)ethylpropiolate (primarily the Z-hydroxy compound); from 2,3-epoxybutane andtetrolic acid there is obtained l-methyl-Z-hydroxypropyl tetrolate; from1,2- epoxypentane and 2-butynoic acid there is obtained a mixture ofl-(hydroxymethyDbutyl and Z-hydroxypentyl 2- butynoate; from ethyleneoxide and naphthalenepropiolic acid there is obtained Z-hydroxyethylnaphthalenepropiolate, etc. The same compounds, of course, can beobtained by mono-esterification with an acetylenic acid, halide oranhydride of the appropriate dihydroxy compound, e.g., 2-hydroxyethylphenylpropiolate is prepared either by the addition reaction of ethyleneoxide with phenylpropiolic acid or by mono-esterification of ethyleneglycol with phenylpropiolic acid. Ring opening of the higher alkyleneoxides, for the purpose of adding the hydroxyalkyl radical, may takeplace at either'of the carbon atoms which are attached to the epoxyoxygen; hence, in order to obtain isomer-free mono-esters it isgenerally advisable to prepare the mono-esters of the higher alkylencglycols by working with the acetylenic acid and the glycol rather thanthe higher alkylene oxide.

The presently provided acetylenie esters of the polyols are stable,well-characterized compounds which are advantageously employed for avariety of industrial and agricultural purposes, e.g., as hardeningagents in synthetic rubber manufacture processes; as plasticizers forvinyl polymers, as mold-release agents in the plastics industry; ashypnotics and soporifics in the pharmaceutical industry; and, ashereinbefore disclosed, as toxicant compositions efiective in preventingor inhibiting the growth of plants and microorganisms.

The acetylenic esters of the invention are of great interest per se asintermediates for the synthesis of a great many compounds. The multipleacetylenic bonds of the esters are very useful in syntheses not onlyowing to the reactivity which generally accompanies unsaturation butalso owing to the activating effect of the ester carbonyl radicals onthe acetylenic bonds. Compounds containing reactive hydrogen add acrossthe triple bond, thus:

The acetylenic bonds are readily halogenated or hydrogenated withproduction of either the fully saturated or olefinically unsaturatedesters, depending upon the reaction conditions. The olefinic esters thusobtained undergo vinyl-type polymerization alone, to give homopolymersof high molecular weight or they copolymerize with other unsaturatedcompounds. The olefinic esters are also readily epoxidized to givecompounds for use in the manufacture of epoxy-type resins. The presentlyprovided acetylenic diesters also undergo addition reactions with waterwhen catalyzed with mercuric sulfate and sulfuric acid to give diketonesvia enolization of intermediately formed hydroxy compounds. According y,to one skilled in the art of organic synthesis, the present compoundsare building materials of great potential.

The invention is further illustrated by, but not limited to, thefollowing examples:

Example I A mixture consisting of 12.4 g. (0.2 mole) of ethylene glycol,30.8 g. (0.44 mole, 10% excess) of propiolic acid, 5 drops of sulfuricacid and 100 ml. of benzene was stirred at reflux under a Dean-Starkapparatus for 5.5 hours. During this time 7.1 ml. of water had collected(98.5% of theory required for diesterification). The reaction mixturewas allowed to cool and then neutralized by adding 0.7 g. of sodiumcarbonate thereto. After standing overnight the reaction mixture wasfreed of solid by filtration, and the filtrate was evaporated atwater-pump pressure to give 32.8 g. of a pale, yellow oil. This wasdistilled to give the substantially pure dipropiolate of ethyleneglycol, B.P. -92 C./0.3 mrn., n 1.4618 which analyzed 57.56% carbon and3.85% hydrogen as against 57.83% and 3.64%, the calculated values.Infrared analysis showed the following structures:

ECH at 3220 cm.- CH aliphatic at 2900 cm.-

CEC 8t 2100 cm- 0 C ester at 1700 cm.- CH; at 1450 cm." C-O-ester at1240 cm."

Example 2 A mixture consisting of 21.0 g. (0.3 mole) of propiolic acid,0.5 g. of tetraethylammonium bromide and ml. of ether was charged to aflask fitted with stirrer, thermometer, gas inlet tube and Dry Icecondenser. To the stirred mixture there was admitted about 14.5 g. (0.33mole) of ethylene oxide along with nitrogen while holding thetemperature of the reaction mixture at from -5 to 0 C. Addition of thegas was carried out over a 1 hour period; during this time there wasnoted no noticeable exothermic reaction. The whole was then stirred at atemperature of 5-15 C. for 1 hour and then allowed to warm slowly toroom temperature under nitrogen. After being allowed to stand at roomtemperature overnight, the reaction mixture, being strongly acidic, wastreated with an additional 5 g. of ethylene oxide at room temperature.During the 20 minute period in which the introduction of the additionalethylene oxide was conducted, the temperature of the reaction rose from16' to 24 C. The ether was then evaporated from the reaction mixture andthere was obtained as residue a pale, yellow oil which upon distillationgave Z-hydroxyethyl propiolate, B.P. 66-68 C./0.5 mm., r1 1.4513analyzing 52.93% carbon and 5.51% hydrogen as against 52.63% and 5.30%the respective calculated values. Infrared analysis gave the followingstructures:

OH at 3400 cm."-

ECH at 3200 cm.'' CECH at 2100 cm." C=O at 1700 cm.- C-O-ester at 1240cm."- CECH at 758 cm.-

CH aliphatic at 2900 cm.-

Example 3 A mixture of 15.4 g. of propiolic acid, 10.4 g. of 2,2-dimethyl-1,3-propanediol, 100 ml. of benzene and 2 ml. of concentratedsulfuric acid was stirred under refluxing conditions in a flask equippedwith a Dean-Stark column. At the end of the reaction, which took about 2hours, it was found that 3.4 ml. of water had been recovered from theoverhead distillate. .The reaction mass was allowed propiolate of2,2-dimethyl-l,S-propanediol, M.P. 63-

64 C., an analyzing 63.25% carbon and 5.85% hydrogen as against 63.45%and 5.81%, the respective calculated values. Infrared analysis-waslikewise confirmatory of the dipropiolate.

Example 4 A mixture of 23.1 g. of propiolic acid, 12 g. of2-(hydroxymethyl)-2-methyl-1,3-propanediol, 100 ml. of benzene and 1 ml.of concentrated sulfuric acid was stirred under refluxing conditions ina flask equipped with a Dean Stark column. After the reaction mass hadrefluxed for a period of 4 hours, it was-found that 6.5 ml. of water hadbeen separated from the overhead distillate. The reaction mass was thencooled and Washed with 50 ml. of 10% aqueous solution of sodiumbicarbonate. The benzene was removed from the reaction mass byevaporation, leaving a yellow oil. Upon standing, the yellow oilcrystallized into long pale yellow needles, M.P. 7881 C.Recrystallization from carbon tetrachloride yielded 23.5 g. of thesubstantially pure tripropiolate of2-(hydroxymethyl)-2-methyl-1,3-propanediol, M.P. 83-84 C., analyzing60.84% carbon and 4.60% hydrogen as against 60.87% and 4.38%, therespective calculated values.

Example 5 A mixture of 70 g. of propiolic acid and 281 g. of

Solvent evaporation followed by distillation in a Vigruex column gave37.6 g'. of the dipropiolate of 2-ethyl-2-butyl- 1,3-propanediol, B.P.116-117 C./0.3-0.2 mm. and analyzing 68.36% carbon and 7.96% hydrogen asagainst 68.16% and 7.63%, the calculated values.

Example 7 This example shows the use of phosphoric acid as catalyst inthe preparation of the dipropiolate of 2,2-dimethyl-1,3-propanediol. Amixture consisting of .7.7 g. (0.11 mole, 10% excess) of propiolic acid,5.2 g. (0.05 mole) of the glycol, 100 ml. of benzene and 5 drops of 85%aqueousphosphoric acid was stirred at reflux for 12 hours in aDean-Stark equipped apparatus. The mixture was refluxed for 15 hours,atthe end of which time no evolution of water was noted. The reactionmixture benzoyl chloride was distilled so that the overhead prodnot ofpropiolyl chloride was charged directly to a flask containing asuspension of 18.0 g. of 4,4'-isopropylidenedicyclohexanol in 200 ml. ofbenzene. When all of the generated propiolyl chloride had beenintroduced, the reaction mixture of 4,4'-isopropylidenedicyclohexanol,propiolyl chloride and benzene was heated to 75 C. At this point all ofthe suspended solids were completely dissolved in the reaction mass. Thereaction mass was held for an additional 1 hour at a temperature of 70C. and then cooled to ambient temperature while being stirred. Benzenewas removed from the reaction mass by evaporation, leaving a pale yellowoil. The oil prodnot was then washed with 250 ml. of boiling hexane togive, on cooling, a colorless solid product. This was then taken maintwo liters of hexane and the resulting solution was evaporated to avolume of 350 ml. On cooling a colorless solid having a melting point of175-200 C. was obtained. Recrystallization from boiling hexane gave thesubstantially pure dipropiolate of 4,4'-isopropylenedicyclohexanol, M.P.200-207 C. and analyzing 73.31% carbon and 7.95% hydrogen as against73.22% and 8.19% the respective calculated values. The constitution ofthe product was confirmed by infrared analys1s.

Example 6 A mixture consisting of 32.0 g. (0.2 mole) of 2-ethyl-2-butyl-1,3-propanediol and 150 ml. of benzene was stirred at reflux toremove any water from the diol. The mixture was then cooled slightly andthere was added thereto a mixture consisting of 30.8 g. (0.44 mole) ofpropiolic acid and 5 drops of sulfuric acid. The reaction mixture wasstirred at reflux for 7 hours. At the end of 5 hours, 5.9 ml. of waterhad evolved and at the end of the 7 hour reflux period, 6.4 ml. of water(84% of that calculated for di-esterification) had evolved. "Ether (100ml.) was added to the reaction mixture and the resulting orange solutionwas washed with 100 ml. of 10% sodium bicarbonate and 100 ml. ofdistilled water.

was then washed with 10% aqueous sodium bicarbonate and with water, andevaporated to give as residue 4.2 g. of a pale, yellow oil whichcomprised the dipropiolate of 2,2-dimethyl-1,3-propanediol.

Example 8 A mixture consisting of 17.3 g. (0.1 mole) of 2,2-bis-(chloromethyl)-1,3-propanediol, 15.4 g. (0.22 mole, 10% excess) ofpropiolic acid, 5 drops of sulfuric acid, and 150 ml. of benzene washeated at reflux under a Dean-Stark apparatus for 12 hours, at the endof which time 5 of water had evolved. The reaction mixture was thenallowed to stand overnight. At the end of this time the precipitatewhich had separated was freed of benzene by evaporation and theresulting buff solid was washed with 150 ml. of 10% aqueous sodiumbicarbonate and two 150 ml. portions of water. It was recrystallizedfrom methanol to give the pale yellow, crude dipropiolate of2,2-bis(chloromethyl)-1,3-propanediol, M.P. 133-35 C. which, aftertreatment with charcoal in methanol and recrystallization, gave thesubstantially pure dipropiolate, M.P. 134-5 C. which analyzed 47.68%carbon and 3.87% hydrogen as against 47.68% and 3.64%, the calculatedvalues. Infrared analysis showed the presence of the followingstructures:

ECH at 3200 cm.- CECH at 2100 cm.- C=0 at 1690 cm.- C-O-ester at 1235cm.-

Example 9 at 5 C. IfOl' 15 minutes and allowed to warm to roomtemperature while stirring. The reaction mixture was then filtered togive a crude colorless solid, M.P. 130-445 C. The filtrate was extractedwith two ml. portions of ether. Evaporation of the ether extract gave awhite solid which was combined with the previously obtained solid, M.P.-145 C. The combined solids were stirred to a homogenous, thin paste viamagnetic stirring, first with 200 ml. of 5% aqueous sodium hydroxide,then with 200 ml. of a saturated aqueous ammonium chloride solution andfinally with two 200 ml. portions of water employing filtration aftereach stirring. The bulk of the solid thus obtained was dissolved in 500ml. of boiling ethanol, filtered while hot to remove traces of pastycolorless material, and cooled slowly to room temperature. Filtrationgave 16.5 g. of colorless fine needles M.P. 150.5-153 C. Twice repeatedrecrystallization from hot ethanol gave the substantially puredipropiolate 0f P,P'-

biphenol M.P. 152-4 C. analyzing 74.47% carbon and 11 3.60% hydrogen asagainst 74.48% and 3.47%, the respective calculated values. Infraredanalysis showed the following structures to be present.

ECH at 3250 cm.-

CECH at 2120 cm.-

C=O ester at 1700 cm:-

(FC aromatic at 1600, 1480 cm.- C-O ester at 1200 cm.-

Example 10 A solution consisting of 13.5 g. (0.153 mole) of propiolylchloride in 50 ml. of benzene was added over a one minute period to amixture consisting of 19.4 g. (0.085 mole) of4,4'-isopropylidenediphenol, 7.0 g. (0.175 mole, 3% excess) of sodiumhydroxide, 300 m1. of water and 100 ml. of benzene, with rapid stirringat a temperature of 5 C. The reaction mixture was stirred at below C.for about minutes, and allowed to stratify, the organic layer wasremoved and the aqueous layer was extracted with two 100 ml. portions ofether. The com bined ether extract and organic layers were washed with100 ml. of water and evaporated to give as residue 30.2 g. of ayellow-orange viscous oil. The bulk of this oil was dissolved in 350 ml.of ether and washed first with 100 ml. of ice-cold 5% aqueous sodiumhydroxide, then with 100 ml. of saturated aqueous ammonium chloride andfinally with two 100 ml. portions of water. Benzene (100 ml.) was addedto the washed product and the resulting solution was evaporated. Theresidual oil was crystallized from absolute ethanol to give thesubstantially pure dipropiolate of 4,4'-isopropylidenediphenol, M.P.126127 C. which upon recrystallization from ethanol gave colorlesscrystals of the substantially pure dipropiolate, M.P. 127-8 C. whichanalyzed 75.70% carbon and 5.02% hydrogen as against 75.89% and 4.85%,the respective calculated values. Infrared analysis showed the presenceof the following structures:

ECH at 3250 cm.-

CECH at 2120 cm.-

p-Subst. at 2000-1650 cm.-

C=O at 1700 cm.-

C=C arom. at 1600, 1500 em.-

C-O-ester at 1220 cm.-

Aromatic subst., ECH, crystallinity at 880-700 cm.-

Example 11 i A mixture consisting of 13.8 g. (0.1 mole) ofp-xylenea,et'-di0l, 15.4 g. (0.22 mole) of propiolic acid, 200 ml. ofbenzene and 0.3 g. of p-toluenesulfonic acid was stirred at reflux for7.5 hours. During this time 3.5 ml. of water (97% of theory) collectedin the Dean-Stark trap which formed a part of the reaction equipment. Tothe resulting reaction mixture there was added 100 ml. of ether, and theorganic material was washed first with 10% aqueous sodium bicarbonatesolution and then with water. Evaporation of the ether and the benzenegave as residue 19.8 g. This was distilled at 0.1 mm. to give thesubstantially pure dipropiolate of p-xylene-u,'-diol, B.P. 147-149C./0.l mm., a pale yellow solid, M.P. 55-61 C., which analyzed 69.50%carbon and 4.38% hydrogen, as against 69.42% and 4.16%, the respectivecalculated values for C H 0 Infrared analysis showed the followingstructures:

CH of HC.= CR at 3250 cm. CEC at 2100 cm.- (.---0 ester, conjugated, at1695 cm.-

0 C-0 0t -O at 1220 cmr C-0 of OR at 950 cm.-

2 adjacent protons at 820 cm.-

12 Example 12 A mixture consisting of 9.7 g. (0.05 mole) oftetramethyl-p-xylene-a,a-diol, 7.7 g. (0.11 mole) of propiolic acid, ml.of benzene and 0.5 g. of p-toluenesulfonic acid was stirred at refluxfor 2 hours in a reaction vessel which was equipped with a Dean-Starkwater trap. During his time, 7.6 g. of water collected in the trap. Thereaction mixture was filtered to give ca. 18 g. of a color less solid,M.P. 182-5 C., and evaporation of the filtrate gave 1.5 g. of a buttsolid, M.P. 179-83 C. Recrystal- 'lization of the combined solids frombenzene gave 14.5

g. (97.5% theoretical yield) of the dipropiolate oftetramethyl-p-xylene-a,a'-diol, fine'needles, M.P. 194-198 C. (withslight blackening), and (after drying in vacuo) analyzing 72.32% carbonand 6.21% hydrogen as against 72.46% and 6.08%, the calculated value for0 11 .0 Infrared analysis showed the following structures:

CH of H-GER at 3200 cm.- CEC at 2100 cm."

O=O ester at 1690 cm.- C-O-ester at 1240 cm.-

Example 13 A mixture consisting of 5.9 g. (0.043 mole) of 4-(2-hydroxyethyl) phenol, 4.2 g. (0.06 mole) of propiolic acid, 100 ml. ofbenzene and 2 drops of sulfuric acid was stirred at reflux under aDean-Stark apparatus for 6 hours. During this time 0.8 ml. (100% oftheory) of water had evolved. After the reaction mixture had attainedroom temperature it was washed with two 100 ml. portions of 10% sodiumbicarbonate and three 100 ml. portions of distilled water. Evaporationyielded 6.7 g. (82% theoretical yield) of a yellow oil which upondistillation gave the substantially pure mono-propiolate of4-(2-hydroxyethyl)phenol, B.P.' /0.2 mm., n 1.5389, analyzing 69.26%carbon and 5.59% hydrogen as against 69.46% and 5.30%, the calculatedvalues. Infrared analysis showed the following structures OH at 3400cm.-

ECH at 3250 cm."

CH arom. at 3000 cm.* CH aliph. at 2900 cm.- CECH at 2120 cm.-

I? C-cster at 1700 cmr (hC arom. at 1600, 1590, 1500 cm." CO-ester+/orphenol at 1240 emf- 2 adj. protons at 830 cm.-

ECH at 760 cm.-

Example 14 A mixture consisting of 32.1 g. (0.22 mole, 10% excess) ofphenylpropiolic acid, 10.4 g. (0.1 mole) of 2,2-dimethyl-l,B-propanediol, five drops of sulfuric acid, and 200 ml. ofbenzene was stirred at reflux under a Dean- Stark trap. At the end of 20hours, 1 ml. of water had collected. Accordingly, 0.5 g. of4-toluenesulfonic acid monohydrate was added to further catalyze thereaction and heating was continued for another 28 hours, at the end ofwhich time 3.5 ml. of water had been collected (theory, 3.6 ml.). Thereaction mixture was then allowed to cool, ether was added, and theresulting solution was extracted first with 100 ml. of water, then with100 ml. of 10% aqueous sodium bicarbonate and finally with '100 ml. ofwater. Evaporation (employing benzene to drive off the water) gave asresidue the. substantially pure bis(phenylpropiolate) of2,2-dimethyl-1,3-propanediol which analyzed 76.37% carbon and 5.85%hydrogen as against 76.65% and 5.59%, the calculated values.

Example 15 excess), 4-toluenesulfonic acid monohydrate (0.5 g.) andbenzene (150 ml.) wasstirred at reflux in an apparatus equipped with aDean-Stark trap. After six hours at reflux, substantially thetheoretical amount of water required for mono-esterification had beencollected. Accordingly, heating was discontinued, the reaction mixturewas allowed to cool and then washed successively with 100 ml. of 10%sodium bicarbonate and 100 ml. of water. After drying in the presence ofbenzene and evaporating there was obtained as residue a pale yellow oilwhich was distilled to give the substantially pure mono-propiolate of4-(2-hydroxyethoxy)phenol, B.P. 147-153 C./0.4 mm., n25/D 1.5442,analyzing 63.11% carbon and 5.3% hydrogen as against 63.91% and 5.23%,the calculated values.

- Example 16 A solution consisting of 14.3 g. (0.16 mole) of propiolylchloride in 100 ml. of benzene was added to a rapidly stirred mixtureconsisting of 16.5 g. (0.15 mole) of hydroquinone, 6.0 g. (0.15 mole) ofsodium hydroxide, 200 ml. of water and 50 ml. of benzene at 5 C. under anitrogen atmosphere. During addition of thepropiolyl chloride solution,which required 1.25 minutes, the temperature of the mixture rose to C.It was stirred at 5 C. for an additional minutes and then allowed toattain room temperature with stirring. Filtration gave 10.3 g. of acolorless solid, M.P. 135-143 C. The filtrate was extracted with two 100ml. portions of ether and the combined extracts were evaporated to givea bull solid,

qtiinone, M.P. 157-158 C. analyzing 67.00% carbon and 2.96% hydrogen asagainst 67.29% and 2.82%, the respective calculated values.

Example 17 -A solution consisting of 16.7 g. (0.19 mole) of propiolylchloride in 100 ml. of benzene was added over a 45 second period to aslowly stirred solution consisting of 21.4 g. (0.1 mole) of resorcinol,8.25 g. (0.206 mole) of sodium hydroxide, 200 ml. water and 50 ml. ofbenzene. temperature of the reaction mixture rose from an initial 5 C.to 15 C. during the addition. The whole was then stirred at 5 C. for 15minutes and then warmed to room temperature within another 15 minutes.The reaction mixture, containing a tlocculent, voluminous, colorlesssolid was filtered and the solid dissolved in 400 ml. of ether. Thefiltrate was extracted with ether and the combined extract and ethersolutionwas washed first with aqueous 5% sodium hydroxide, then withsaturated aqueous ammonium chloride and finally with water. To thewashed material there was added 100 ml. of benzene and the whole wasevaporated in vacuo to give a colorless oil which solidified uponstanding to give the dipropiolate of resorcinol, M.P. 60.5-62' C.analyzing 67.24% carbon and 3.09% hydrogen as against 67.29% and 2.82%,the respective calculated values.

Example 18 A mixture consisting of 17.6 g. (0.2 mole) of2-butene-1,4-diol, 30.8 g. (0.44 mole, 10% excess) of propiolic acid and150 ml.- of benzene was stirred at reflux under a Dean-Stark apparatusfor one hour. At the end of that time the reaction mixture was cooledslightly and 0.5 g. of 4-toluenesulfonic acid was added. Heating withstirring was then conducted for 24 hours. After allowing the reactionmixture to cool it was washed first with 100 ml. of 10% aqueous sodiumbicarbonate and then with two 100 ml. portions of water. The washedreaction mixture was diluted with 100 ml. of benzene and the wholeevaporated to give as residue 8.4 g. of

, 14 104-106 C./0.l mm., 1: 1.4798. Infrared analysis showed thepresence of the following structures:

ECH at 3300 cm:-

CH unsat. at 3050 cm.- CH aliph. at 2975 cm." CECH at 2125 cm. 0:0 at1725 cm.- C--0-ester at 1220 cm.-- ECH at 755 emf- Example 19 ous sodiumbicarbonate and two ml. portions of water. To the washed product therewas then added-100 ml. of benzene and the whole was subjected toevaporation, first at water-pump pressure and then at. high vacuurn.Removal of the solvents in.this manner gave as residue 35.6 g. of acolorless, gel-like solid which upon twice repeated crystallization fromethanol gave the sub- .stantially pure tetrapropiolate ofpentaerythritol, M.P. 108.51l0 C., analyzing 58.89% carbon and 3.76%

hydrogen, as against 59.31% and 3.51%, the calculated values. Infraredanalysis showed the following structures:

ECH at .3400, 3375 cm.- CECH at 2125 cm.-

C=O at 1725 cm." I C-O-ester at 1240 cm:-

' Example 20 This example shows testing of the following compoundsagainst the fungus Aspergillus niger:

(I) Tripropiolate of 2-(hydroxymethyl)-2-methyl-l,3-

propanediol (Example 4) (H) Dipropiolate of 2,2-dimethyl-1,3-propanediol(Example 3) I (HI) Dipropiolate of p-xylenea,u'-diol (Example 11) Thefollowing procedure was used:

An inoculum preparation of Aspergillus niger SN-lll was prepared byadding 10 ml. of sterile distilled water to a 7-day old, Sabouraudsdextrose agar slant culture thereof and dislodging the organisms intothe water with a transfer needle.

Culture media was prepared by respectively adding 18 ml. of Sabouraudsdextrose agar to 18 x mm. straight side test tubes, capping with metalculture tube caps, and sterilizing in an autoclave for fifteen minutesat 121 C.

Respective stock solutions of the test compounds were prepared bydissolving 100 mg. of said test compound in 10 m1. of acetone:respective 1% acetone solutions of the compounds were thus obtained.

Using a sterile 5 ml. pipette, 2 ml. of said 1% solutions wererespectively transferred to a tube of melted, sterile culture mediaprepared as described above. Dilutions of 1 part of test compound per1,000 parts of agar resulted. The thus-diluted agars were then pouredinto sterile Petri dishes and allowed to harden. Two dishes of agarcontaining the same concentration of acetone but none of the testcompound were also prepared and allowed to harden; these were to be usedfor controls.

The plates of agar were then respectively inoculated with one drop ofthe above-described inoculum preparation. Examination of the platesafter a five-day incubation period showed no growth of the Aspergillusniger in those of the plates which contained either compound 1, compoundH or compound HI, whereas profuse growth 1 of the Aspergillus niger wasnoted in both of the control plates.

Example 21 This example shows testing of the following compounds againstthe bacteria Staphylococcus aureus and Salmonella typhosa.

(I) Tripropiolate of 2-(hydroxymethy1)-2-methyl-l,3-

propanediol (Example 4) (II) Dipropiolate of2,2-dimethyl-1,3-propanediol (Example 3) (III) Dipropiolate ofp-xylene-a,a'-diol (Example 11) The following procedure was used:Respective 1% acetone solutions of the above compounds were prepared andadded to sterile, melted nutrient agar to give an 0.1% concentration ofthe test compound in the agar. These agar solutions of the testcompounds were then respectively poured into Petri dishes and allowed toharden. These plates as well as duplicate controls (plates of sterilenutrient agar containing the same concentration of acetone but none ofthe test compound) were respectively inoculated with either theStaphylococcus aureus or the Salmonella typhosa, and incubated for twodays at 37 C. At the end of that time, inspection of the plates showedno growth of either bacillus on those of the plates which containedeither Compound I, Compound II or Compound HI whereas profuse growth ofboth of the test organisms was noted on the controls.

Example 22 Testing of the Z-hydroxyethyl propiolate of Example 2, usingsubstantially the procedure described in Examples 14 and 15, except thatthe propiolate was used at a concentration of 0.01% showed it to inhibitgrowth of the following organisms:

S. aureus B. cereus v. mycozdes B. 'ammoniagenes E. col-i E.atrosepctica S. typhosa Ps. aeruginosa B. subtilis A. niger P. expansumF. annosus C. pilfera A. oryzae C. herbarium M. verrucaria M. fructicolaL. traber Example 23 The tripropiolate ofZ-(hydroxymethyl)-2-methyl-1,3- propanediol of Example 4 was testedagainst the fungi Alternaria solani (the causal organism of tomatoblight) and against Colletotrichum lagenarium, the causal agent ofcucumber anthracnose. The testing was conducted by spraying to run-off,four uniform, 3-week old Green Prolific cucumber plants with an 0.1%aqueous emulsion of said tripropiolate and spraying, also to run-off,four uniform Bonny Best tomato plants at the 4-5 leaf stage with an0.01% aqueous emulsion of said tripropiolate, allowing the sprayedplants to dry, subsequently inoculating the cucumber plants with saidcucumber fungus and the tomato plants with said tomato fungus,maintaining 'the thus sprayed and inoculated plants in a moisturechamber at70 F. for 36 hours, then removing them to a greenhouse benchand periodically inspecting the plants for incidence of the diseaseduring a 5-day period. At the end of this period, the plants wereobserved to be flourishing and free of disease. 0n the other hand,controls which had been similarly inoculated and maintained weredisease-ridden.

Similar testing of the dipropiolate of 2-ethyl-2-butyl- 1,3-propanediolof Example 6 and of the dipropiolate of p-xylene-a,a'-diol of Example llagainst said tomato blight fungus at an 0.1% concentration showed thesedipropiolates to suppress completely the growth of said fungus.

Example 24 The dipropiolate of ethylene glycol of Example 1, thedipropiolate of 2,2-dimethyl-1,3-propanediol of Example 3, thedipropiolate of 2-ethyl-2-butyl-1,3-propanediol of Example 6, and thetripropiolate of.2-(hydroxymethyl)-1,3-propanediol of Example 4 weretested against the soil fungus Rhizoctonia solani. Testing was conductedby adding to soil which had been uniformly infected with the fungus aquantity of either the dipropiolate or the tripropiolate which was 0.01%the weight of the soil, thoroughly mixing the whole, incubating at 25 C.for 24 hours, seeding pots of the incubated soil with cotton andcucumber seeds, maintaining the seeded pots for 48 hours at 70 F. and ata high relating humidity (96 98%), removing the pots to the greenhouse,maintaining them there for 2 weeks, and inspecting them for number ofseedlings emerged and the condition of the shoots and roots thereof. Asimilar testing procedure was conducted with controls, i.e., similarlyinoculated soil which had not been chemically treated. A very poorpercent emergence and a stunted diseased condition of those of theplants which had emerged was noted in the controls, whereas excellentgermination and plant growth was observed in the pots of inoculated soilwhich had been treated with said dipropiolate or tripropiolate.

Similar testing of the dipropiolate of ethylene glycol of Example 1, ofthe dipropiolate of 2-ethyl-2-butyl-l,3- propanediol of Example 6 and ofthe dipropiolate of p-xylene-a,a'-diol of Example 11 against the soilfungus Pythium ultimum showed these dipropiolates to inhibit completelythe growth of the Pythium at a concentration of 0.01%.

The present acetylenic esters are characterized by a high degree ofefficacy in that they inhibit growth of bacteria and fungi at even verylow concentrations. They are characterized by having a broad spectrum ofbactericidal activity, e.g. the dipropiolates are effective against thevariety of bacteria as shown in Examples 21 and 22, and they inhibit avariety of fungi such as the causative organisms of cucumber and tomatoleaf spot and blight, apple scab, citrus mold, rose leaf spot, wheatrust, etc. Biological toxicant compositions containing the presentcompounds are advantageously formulated by first preparing a solutionthereof in an organic solvent and then adding the resulting solution towater containing an emulsifying agent to form an oil-in-water emulsionBecause of their effectiveness, they are present in the toxicantcompositions in only very small concentrations, for example, inconcentrations of from 0.0001 percent to 1.0 percent by weight of thetotal weight of the emulsion. Emulsifying agents which may be employedare those customarily used in the art for the preparation of oilin-wateremulsions. Examples of emulsifying agents which may be used includealkylbenzenesulfonates, long chained polyalkylene glycols, long chainedalkylsulfosuccinates, etc.

While the present compounds are most advantageously employed asbiological toxicants by incorporating them into an emulsion as hereindescribed, they may also be incorporated into solid carriers such asclay, talc, pumice or bentonite to give compositions which may beapplied 17 either to infested areas or tolocale which may be subjectedto infestation. They may also be dissolved in liquefied gases such asthe fluorochlorooethanes or methyl chloride and applied from aerosolbombs containing the solution.

- What we claim is:

1. An ester of the formula (Ho)n'R(oi :cE0z)m where R is selected fromthe class consisting of hydrocarbon radicals and halohydrocarbonradicals of from 2 to 18 carbon atoms and is linked through diversecarbon atoms thereof to the remainder of the molecule of which it formsa part, it is an integer of from 0 to 3, m is an integer of from 1 to 4and the sum of n plus m is from 2 to 4, and Z is selected from the classconsisting of hydrogen, alkyl radicals of from 1 to 5 carbon atoms andaryl radicals of from 6 to 10 carbon atoms.

2. An ester of the formula (HO) n R' (O CECH)m where R is a hydrocarbonradical of from 2 to 18 carbon atoms and is linked through diversecarbon atoms thereof to the remainder of the molecule of which it formsa part, n is an integer of from 0 to 3, m is an integer of from 1 to 4,and the sum of n plus m is from 2 to 4.

3. An ester of the formula 0 H0 ..-R"- 0bc- -oH... where R" is analkylene radical of from 2 to 18 carbon atoms and is linked throughdiverse carbon atoms thereof to the remainder of the molecule of whichit forms a part, n is an integer of from 0 to 3, m is arr/integer offrom 1 to 4 and the sum of n plus m is from 2 to 4.

4. An ester of the formula 0 HOR'-OO.P1CECH wherein R is a hydrocarbonradical of from 2 to 18 carbon carbon atoms and is linked throughdiverse carbon atoms thereof to the remainder of the molecule of whichit forms a part.

5. An ester of the formula where R is a hydrocarbon radical of from 2 to18 carbon atoms and is linked through diverse carbon atoms thereof tothe remainder of the molecule of which it forms a part.

6. Dipropiolate of ethylene glycol.

7. 2-hydroxyethyl propiolate.

8. Dipropiolate of 2,2-dimethyl-1,3-propanediol.

9. Dipropiolate of 4,4'-isopropylidenedicyclohexanol.

10. Dipropiolate of p,p'-biphenol.

References Cited in the tile of this patent UNITED STATES PATENTS2,082,790 Cherry June 8, 1937 2,290,649 Macallum July 21, 1942 2,370,572Muskat et al Feb. 27, 1945 2,484,487 Caldwell Oct. 11, 1949 2,600,275Smith June 10, 1952 2,692,256 Bauer et a1. Oct. 19, 1954 FOREIGN PATENTS118,774 Australia Aug. 7, 1944 OTHER REFERENCES Heaton et al.: J.A.C.S.,vol. 71, pp. 2948-2949 (1949).

1. AN ESTER OF THE FORMULA 